Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

The development of automated methods for the determination of trace concentrations of carbomate pesticides in water using solid sorbent pre-concentration methods and high performance liquid chromatography /

Several automated reversed-phase HPLC methods have been developed to determine trace concentrations of carbamate pesticides (which are of concern in Ontario environmental samples) in water by utilizing two solid sorbent extraction techniques. One of the methods is known as on-line pre-concentration'. This technique involves passing 100 milliliters of sample water through a 3 cm pre-column, packed with 5 micron ODS sorbent, at flow rates varying from 5-10 mUmin. By the use of a valve apparatus, the HPLC system is then switched to a gradient mobile phase program consisting of acetonitrile and water. The analytes, Propoxur, Carbofuran, Carbaryl, Propham, Captan, Chloropropham, Barban, and Butylate, which are pre-concentrated on the pre-column, are eluted and separated on a 25 cm C-8 analytical column and determined by UV absorption at 220 nm. The total analytical time is 60 minutes, and the pre-column can be used repeatedly for the analysis of as many as thirty samples. The method is highly sensitive as 100 percent of the analytes present in the sample can be injected into the HPLC. No breakthrough of any of the analytes was observed and the minimum detectable concentrations range from 10 to 480 ng/L. The developed method is totally automated for the analysis of one sample. When the above mobile phase is modified with a buffer solution, Aminocarb, Benomyl, and its degradation product, MBC, can also be detected along with the above pesticides with baseline resolution for all of the analytes. The method can also be easily modified to determine Benomyl and MBC both as solute and as particulate matter. By using a commercially available solid phase extraction cartridge, in lieu of a pre-column, for the extraction and concentration of analytes, a completely automated method has been developed with the aid of the Waters Millilab Workstation. Sample water is loaded at 10 mL/min through a cartridge and the concentrated analytes are eluted from the sorbent with acetonitrile. The resulting eluate is blown-down under nitrogen, made up to volume with water, and injected into the HPLC. The total analytical time is 90 minutes. Fifty percent of the analytes present in the sample can be injected into the HPLC, and recoveries for the above eight pesticides ranged from 84 to 93 percent. The minimum detectable concentrations range from 20 to 960 ng/L. The developed method is totally automated for the analysis of up to thirty consecutive samples. The method has proven to be applicable to both purer water samples as well as untreated lake water samples.

Genesis and distribution of Mississippi Valley-type ore assemblages in Middle Silurian strata, Niagara Peninsula, Ontario /

Presently non-commercial occurrences of Mississippi Valley-type ore assemblages in the Middle Silurian strata of the Niagara Peninsula have been studied. Based on this detailed study, a new poly-stage genetic model is proposed which relates ore mineralization in carbonate environments to the evolution of the sedimentary basin. Sulphide ore mineralization occurred during two episodes: 1. During the late diagenesis stage, which is characterized by compaction-maturation of the sediments, the initial mineralization took place by upward and outward movement of connate waters. Metals were probably supplied from all the sediments regardless of their specific lithologies. However, clay minerals were possibly the main contributors. The possible source of sulphur was from petroleum-type hydrocarbons presently mixed with the sediments at the site of ore deposition. Evidence for this is the fact that the greatest abundance of ore minerals is in petroliferous carbonates. The hydrocarbons probably represent liquids remaining after upward migration to the overlying Guelph-Salina reservoirs. The majority of sphalerite and galena formed during this period, as well as accessory pyrite, marcasite, chalcopyrite, chalcocite, arsenopyrite, and pyrrhotite; and secondary dolomite, calcite, celestite, and gypsum. 2. During the presently ongoing surface erosion and weathering phase, which is marked by the downward movement of groundwater, preexisting sulphides were probably remobilized, and trace amounts of lead and zinc were leached from the host material, by groundwaters. Metal sulphides precipitated at, or below, the water table, or where atmospheric oxygen could raise the Eh of groundwaters to the point where soluble metal complexes are unstable and native sulphur co-precipitates with sphalerite and galena. This process, which can be observed today, also results in the transport and deposition of the host rock material. Breakdown of pre-existing sulphide and sulphate, as well as hydrocarbon present in the host rock, provided sulphur necessary for sulphide precipitation. The galena and sphalerite are accompanied by dolomite, calcite, gypsum, anglesite, native sulphur and possibly zincite.

Investigation of the composition of linear alkylbenzenes with emphasis on the identification and quantitation of some trace compounds using GS/MS system in both electron impact and chemical ionization modes

Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.

Synthesis of nanoporous materials for preconcentration and determination of trace elements by ICP-AES ; Investigation and elimination of the memory effects of mercury, gold, silver and boron in ICP-AES

Nanoporous materials with large surface area and well-ordered pore structure have been synthesized. Thiol groups were grafted on the materials' surface to make heavy metal ion pre-concentration media. The adsorption properties ofthe materials were explored. Mercury, gold and silver can be strongly adsorbed by these materials, even in the presence of alkaline earth metal ion. Though the materials can adsorb other heavy metal ions such as lead and copper, they show differential adsorption ability when several ions are present in solution. The adsorption sequence is: mercury> == silver> copper » lead and cadmium. In the second part of this work, the memory effects of mercury, gold, silver and boron were investigated. The addition of 2% L-cysteine and 1% thiourea eliminates the problems of the three metal ions completely. The wash-out time for mercury dropped from more than 20 minutes to 18 seconds, and the wash-out time for gold decreased from more than 30 minutes to 49 seconds. The memory effect of boron can be reduced by the use of mannitol.

The determination of the helium discharge detector response to fixed gases

The Beckman Helium Discharge Detector has been found to be sensitive to the fixed gases oxygen, nitrogen, and hydrogen at detection levels 10-100 times more sensitive than possible with a Bow-Mac Thermal Conductivity Detector. Detection levels o~ approximately 1.9 E-4 ~ v/v oxygen, 3.1 E-4 ~ v/v nitrogen, and 3.0 E-3 ~ v/v hydrogen are estimated. Response of the Helium Discharge Detector was not linear, but is useable for quantitation over limited ranges of concentration using suitably prepared working standards. Cleanliness of the detector discharge electrodes and purity of the helium carrier and discharge gas were found to be critical to the operation of the detector. Higher sensitivities of the Helium Discharge Detector may be possible by the design and installation of a sensitive, solid-state electrometer.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Investigating Microbial Trace-fossils and Abiotic Alteration in Hydrovolcanic Tuffs of the Fort Rock Volcanic Field, Oregon

Microbial ichnofossils in volcanic rocks provide a significant record of subsurface microbes and potentially extraterrestrial biosignatures. Here, the textures, mineralogy, and geochemistry of two continental basaltic hydrovolcanic deposits - Reed Rocks and Black Hills - in the Fort Rock Volcanic Field (FRVF) are investigated. Methods include petrographic microscopy, micro and powder X-ray diffraction, SEM/BSE/EDF imaging, energy dispersive spectroscopy, stable isotopes, and X-ray fluorescence. Petrographic analysis revealed granular and tubular textures with biogenic morphologies that include terminal enlargements, septate divisions, branching forms, spiral filaments, and ovoid bodies resembling endolithic microborings described in ocean basalts. They display evidence of behaviour and a geologic context expressing their relative age and syngenicity. Differences in abiotic alteration and the abundance/morphotype assemblage of putative microborings between the sites indicate that water/rock ratio, fluid composition and flux, temperature and secondary phase formation are influences on microboring formation. This study is the first report of reputed endolithic microborings in basalts erupted in a continental lacustrine setting.

Validación de un método analítico para la determinación de contaminantes orgánicos volátiles en agua por cromatografía de gases

Tesis (Maestría en Ciencias con Especialidad en Química Analítica Biomédica) UANL

Propuesta didáctica : programa interactivo para el aprendizaje del tema de gases en el sistema abierto

Tesis (Maestría en la Enseñanza de la Ciencia con Especialidad en Química) UANL

Estimación de la eficiencia en el uso del agua mediante mediciones de intercambio de gases y análisis de crecimiento en tres especies cultivadas

Tesis (Maestría en Ciencias en Producción Agrícola) UANL

Dinámica de gases aplicada a las toberas

Tesis (Maestro en Ciencias de la Ingeniería Mecánica con Especialidad en Térmica y Fluidos - Universidad Autónoma de Nuevo León, 1999

Modelado y control de recirculación de gases de escape en motores a inyección de combustible

Tesis (Maestro en Ciencias de la Ingeniería Eléctrica con Especialidad en Control) UANL, 2000.

Análisis de hidrocarburos aromáticos policíclicos en agua potable mediante cromatografía de gases con detector selectivo de espectrometría de masas desarrollo y validación de un método anlítico por Nora Emma Díaz Moroles

Tesis (Maestría en Ciencias Químicas con Especialidad en Química Analítica) U.A.N.L.